764-42-1Relevant articles and documents
Associative Covalent Relay: An Oxadiazolone Strategy for Rhodium(III)-Catalyzed Synthesis of Primary Pyridinylamines
Yu, Xiaolong,Chen, Kehao,Wang, Qi,Guo, Shan,Zha, Shanke,Zhu, Jin
supporting information, p. 5222 - 5226 (2017/04/27)
A relay formalism is proposed herein for categorizing the interplay among reactants, target product, and catalytic center in transition-metal catalysis, an important factor that can dictate overall catalysis viability and efficiency. In this formalism, transition-metal catalysis can proceed by dissociative relay, associative covalent relay, and associative dative relay modes. An intriguing associative covalent relay process operates in rhodium(III)-catalyzed oxadiazolone-directed alkenyl C?H coupling with alkynes and allows efficient access to primary pyridinylamines. Although the primary pyridinylamine synthesis mechanism is posteriori rationalized, the relay formalism formulated herein can provide an important mechanistic conceptual framework for future catalyst design and reaction development.
Synthesis and characterization of an A2BC type phthalocyanine and its visible-light-responsive photocatalytic H2 production performance on graphitic carbon nitride
Guo, Yingying,Song, Shuaishuai,Zheng, Ya,Li, Renjie,Peng, Tianyou
supporting information, p. 14071 - 14079 (2016/11/05)
A highly asymmetric A2BC type zinc phthalocyanine (Zn-di-PcNcTh) has been designed and synthesized. The Zn-di-PcNcTh used a π electron rich thiophene ring in place of the benzenoid rings of phthalocyanine which acted as an electron donor, diphenylphenoxy substituents to retard aggregation and a carboxyl-naphthalene unit as an electron acceptor. The asymmetric phthalocyanine shows a strongly split Q-band and wide spectral absorption in the visible/near-IR light region, which can extend the spectral response region of graphitic carbon nitride (g-C3N4) from ～450 nm to more than 800 nm. By using it as a sensitizer of 1.0 wt% Pt-loaded graphitic carbon nitride (g-C3N4), the experimental results indicate that Zn-di-PcNcTh-Pt/g-C3N4 shows a H2 production efficiency of 249 μmol h-1 with an impressive turnover number (TON) of 9960.8 h-1 under visible light (λ ≥ 420 nm) irradiation, much higher than that of pristine Pt/g-C3N4. Owing to the introduction of a highly bathochromic shift of 3,4-dicyanothiophene and the valuable "push-pull" effect from the thiophene (electron donor) to the carboxyl-naphthalene (electron acceptor) unit, Zn-di-PcNcTh/g-C3N4 gives an extremely high apparent quantum yield (AQY) of 2.44%, 3.05%, and 1.53% under 700, 730, and 800 nm monochromatic light irradiation, respectively, under optimized photocatalytic conditions.
Common origins of RNA, protein and lipid precursors in a cyanosulfidic protometabolism
Patel, Bhavesh H.,Percivalle, Claudia,Ritson, Dougal J.,Duffy, Colm D.,Sutherland, John D.
, p. 301 - 307 (2015/04/14)
A minimal cell can be thought of as comprising informational, compartment-forming and metabolic subsystems. To imagine the abiotic assembly of such an overall system, however, places great demands on hypothetical prebiotic chemistry. The perceived differences and incompatibilities between these subsystems have led to the widely held assumption that one or other subsystem must have preceded the others. Here we experimentally investigate the validity of this assumption by examining the assembly of various biomolecular building blocks from prebiotically plausible intermediates and one-carbon feedstock molecules. We show that precursors of ribonucleotides, amino acids and lipids can all be derived by the reductive homologation of hydrogen cyanide and some of its derivatives, and thus that all the cellular subsystems could have arisen simultaneously through common chemistry. The key reaction steps are driven by ultraviolet light, use hydrogen sulfide as the reductant and can be accelerated by Cu(I)-Cu(II) photoredox cycling.
PROCESS FOR PRODUCING ISOTHIAZOLE DERIVATIVE
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Page/Page column 6, (2012/03/10)
A process for producing 3,4-dichloro-5-cyanoisothiazole represented by a general formula (3): the process comprising: reacting a nitrile compound represented by a general formula (1): (wherein “n” denotes an integer of 0 to 2), with sulfur chloride represented by a general formula (2): [Chemical Formula 18] SmCl2 ??(2) (wherein “m” represents an integer of 1 to 2), or a mixture thereof in an aprotic polar solvent. There is provided a process for producing 3,4-dichloro-5-cyanoisothiazole, which is capable of suppressing by-production of a waste, without using a raw material having a having a strong toxicity; and is capable of providing a product having a higher purity in a high yield and efficiency in an industrial scale, in a simple manner.
2 H-azirines from a concerted addition of alkylcarbenes to nitrile groups
Knoll, Wolfgang,Mieusset, Jean-Luc,Arion, Vladimir B.,Brecker, Lothar,Brinker, Udo H.
supporting information; experimental part, p. 2366 - 2369 (2010/07/13)
Photolysis of aziadamantanes in the presence of fumaronitrile (FN) unexpectedly afforded conjugated 2H-azirines resulting from addition of the carbene to the CN triple bond. This represents the first example of a direct azirine formation starting from an alkylcarbene for which a concerted pathway is postulated. The novel outcome of the reaction is favored by the prior formation of a carbene-alkene complex, a type of adduct that only recently has been described.
Synthesis, structures, and reactivity of kinetically stabilized anthryldiphosphene derivatives
Tsurusaki, Akihiro,Nagahora, Noriyoshi,Sasamori, Takahiro,Matsuda, Kazunari,Kanemitsu, Yoshihiko,Watanabe, Yasuaki,Hosoi, Yoshinobu,Furukawa, Yukio,Tokitoh, Norihiro
body text, p. 456 - 478 (2010/07/04)
The first stable anthryldiphosphenes, 1 and 2, were synthesized by utilizing kinetic stabilization of 2,4,6- tris[bis(trimethylsilyl)methyl]phenyl (Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl] phenyl (Bbt) groups, and were characterized by spectroscopic and X-ray crystallographic analyses. The UVvisible spectroscopic data suggested the electronic communication between the anthryl moiety and the P=P unit. It was found that TbtP=P(9- Anth) (1a: 9-Anth = 9-anthryl) showed weak fluorescence in hexane solution. Furthermore, the reactivities of anthryldiphosphene 1 with a chromium complex, chalcogenation reagents, a diene, and electron-deficient olefins have been revealed.
Olefin self-cross-metathesis catalyzed by the second-generation Grubbs carbene complex in room temperature ionic liquids
Ding, Xiong,Lv, Xianhai,Hui, Bin,Chen, Zhijuan,Xiao, Minliang,Guo, Baoshou,Tang, Wenming
, p. 2921 - 2924 (2007/10/03)
Olefin self-cross-metathesis (CM) reactions catalyzed by the second-generation Grubbs carbene complex have been compared in dichloromethane and two kinds of selected room temperature ionic liquids (RTILs). Both the catalyst and the ionic liquids could be simply recovered and reused for at least four cycles just with a little drop in activity. Significant enhancements in the reactivity, yield and reaction rate were achieved.
Highly active phosphine-free carbene ruthenium catalyst for cross-metathesis of acrylonitrile with functionalized olefins
Bai, Chen-Xi,Zhang, Wen-Zhen,He, Ren,Lu, Xiao-Bing,Zhang, Zhi-Qiang
, p. 7225 - 7228 (2007/10/03)
The carbene ruthenium complex [1,3-bis(2,6-dimethylphenyl)-4,5- dihydroimidazol-2-ylidene](C5H5N)2(Cl) 2RuCHPh (8) was prepared by the reaction of [1,3-bis (2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene](PPh3)(Cl) 2RuCHPh (7) with pyridine and used as a highly effective catalyst for the cross-metathesis of acrylonitrile with various functionalized olefins.
Lewis-acid assisted cross metathesis of acrylonitrile with functionalized olefins catalyzed by phosphine-free ruthenium carbene complex
Bai, Chen-Xi,Lu, Xiao-Bing,He, Ren,Zhang, Wen-Zhen,Feng, Xiu-Juan
, p. 4139 - 4142 (2007/10/03)
The exchange of the PPh3 ligand in the complex [1,3-bis(2,6-dimethylphenyl)4,5-dihydroimidazol-2-ylidene](PPh 3)-(Cl)2Ru=CHPh (7) for a pyridine ligand at ambient temperature leads to the formation of the stable phosphine-free carbene ruthenium complex [1,3-bis(2,6-dimethylphenyl)4,5-dihydroimidazol-2-ylidene] (C5H5N)2(Cl)2 Ru=CHPh (8). The resulted ruthenium complex exhibits highly catalytic activity for the cross metathesis of acrylonitrile with various functionalized olefins under mild conditions, and its activity can be further improved by the addition of a Lewis acid such as Ti(O′Pr)4. In the mixture products, the Z-isomer predominates. The Royal Society of Chemistry 2005.
Microwave spectra and molecular structures of (Z)-pent-2-en-4-ynenitrile and maleonitrile
Halter,Fimmen,McMahon,Peebles,Kuczkowski,Stanton
, p. 12353 - 12363 (2007/10/03)
Accurate equilibrium structures have been determined for (Z)-pent-2-en-4-ynenitrile (8) and maleonitrile (9) by combining microwave spectroscopy data and ab initio quantum chemistry calculations. The microwave spectra of 10 isotopomers of 8 and 5 isotopomers of 9 were obtained using a pulsed nozzle Fourier transform microwave spectrometer. The ground-state rotational constants were adjusted for vibration-rotation interaction effects calculated from force fields obtained from ab initio calculations. The resultant equilibrium rotational constants were used to determine structures that are in very good agreement with those obtained from high-level ab initio calculations (CCSD(T)/cc-pVTZ). The geometric parameters in 8 and 9 are very similar; they also do not differ significantly from the all-carbon analogue, (Z)-hex-3-ene-1,5-diyne (7), the parent molecule for the Bergman cyclization. A small deviation from linearity about the alkyne and cyano linkages is observed for 7-9 and several related species where accurate equilibrium parameters are available. The data on 7-9 should be of interest to radioastronomy and may provide insights on the formation and interstellar chemistry of unsaturated species such as the cyanopolyynes.
